Oil-soluble multifunctional detergent-dispersant comprising an amide of a polyamine and an alkaryl keto acid

ABSTRACT

An oil-soluble additive useful for improving the properties of a fuel oil, a lubricating oil, a heating oil, a gasoline or the like is prepared by heating an aliphatic polyamine or amino alcohol with an alkylated aryl carboxylic acid at a temperature that causes the splitting out of water. The carboxylic acid is prepared by thermal diene addition of an alkylated aromatic hydrocarbon such as paraffin-wax-alkylated naphthalene, or of a ring-substituted hydroxy, amino, or vinyl derivative of such hydrocarbon, with an unsaturated monobasic acid, or with an unsaturated polybasic acid or its anhydride, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, or the like. The additive can be modified by treatment with phosphorous acid.

United States Patent US. Cl. 260-558 Claims ABSTRACT OF THE DISCLOSURE An oil-soluble additive for improving the properties of a fuel oil, lubricating oil, heating oil or the like, particularly with respect to sludge dispersancy and detergency, is prepared by heating an aliphatic polyamine with an aralkyl keto acid at a temperature that causes splitting out of water to form an amide. The keto acid can be prepared by condensing an alkylated aryl compound having an alkyl group of from 12 to about 32 carbon atoms with a dibasic acid, a dibasic acid anhydride, or a dibasic acid halide, having a total of from 4 to 20 carbon atoms. For example, paraflin-wax-alkylated naphthalene is condensed with maleic anhydride, and the resulting keto acid is reacted with tetraethylene pentamine.

DESCRIPTION OF THE INVENTION This application is a continuation-in-part of Ser. No. 354,756, filed Mar. 25, 1964, and now abandoned.

This invention concerns improved oil-soluble nitrogencontaining additives capable of serving multiple functions in oil compositions of the class of fuel oils, heating oils, and lubricating oils. These additives can be characterized as amide derivatives or combined amide and Schiff base derivatives of alkaryl keto acids. The invention is also directed to the preparation of these additives and to oil compositions containing them.

For satisfactory lubrication of modern high compression piston type internal combustion engines, it is necessary to lubricate those engines with a crankcase oil that will provide a high degree of engine cleanliness and thus promote longer engine life. This requires a heavy duty detergent type of lubricating oil containing additives that will impart good detergency, efiicient sludge dispersing action and high oxidation resistance. It has heretofore been the practice to supply detergency and dispersancy to heavy duty internal combustion engine lubricants by the use of metallic compounds such as metal salts of organic sulfonic acids, metal salts of alkylated phenols, metal salts of alkyl phenol thioethers, metal alcoholates, colloidal dispersions of carbonates and the like. Usually alkaline earth metal salts are employed for this purpose. More recently it has been recognized that metal-free additives, or at least additives that are relatively low in metal content, are preferred to the conventional metal-containing additives because the latter materials leave an ash residue which tends to accumulate in the combustion chamber of the engine and there cause pre-ignition, spark plug fouling, valve burning and similar undesirable conditions. For this reason an effective dispersant that is ash-free is preferable to an ashforming detergent additive such as an alkaline earth metal salt of the types mentioned above. Ash-free dispersants are also of advantage in fuel oil compositions and diesel fuels.

It has now been found in accordance with the present invention that effective ash-free mineral-oil-soluble detergent inhibitors and dispersants that also possess pour-point depressant properties can be prepared by reacting certain ice alkaryl keto acids, derived from alkylated aromatic compounds, with aliphatic polyamines under conditions that favor amide formation.

The keto acids that are employed in this invention may be characterized by the following general formula:

In the above formula R is at least one aliphatic hydrocarbon radical having in the range of from 12 to about 32 carbon atoms and R is a hydrocarbon radical having in the range of from 2 to about 18 carbon atoms, preferably from about 2 to 6 carbon atoms. The symbol Ar in the above formula is an aromatic radical, having in the range of 6 to 16 carbon atoms, which may be a cyclic hydrocarbon, a short-chain-alkylated cyclic hydrocarbon, or a hydroxy derivative of either, such as phenol, a C to C alkyl phenol (e.g. tertiary butyl phenol, methyl phenol, etc.), naphthol, benzene, toluene, xylene, other C to C alkyl ben'zenes, naphthalene, anthracene, or phenanthrene. Preferably Ar represents naphthalene. The symbol R in the above formula is preferably derived from paraflin wax hydrocarbons, i.e. by alkylating naphthalene, benzene, phenol, or the like with halogenated paraffin wax, although the alkylation may be eflfected with other halogenated paraffin hydrocarbons in the C to about C range, e.g. chlorinated gas oil, chlorinated kerosene, 1,2-dichloro dodecane, monobromo cetane, etc. Paraffin wax is a petroleum product that is a mixture of aliphatic hydrocarbons mostly in the C to C range. The hydrocarbon distribution will depend on the particular melting point grade of wax used. Thus a l27 F. melting point wax will predominate in about C to C aliphatic hydrocarbons.

Alkylation of the C to C aromatic hydrocarbon or related monohydroxy derivative can be effected not only by condensation with a halogenated aliphatic hydrocarbon as stated above, but also by Friedel-Crafts condensation with an olefin, as for example, by alkylating benzene or toluene with tetrapropylene or with a C alpha olefin obtained by cracking a paraffin wax fraction.

The preparation of a keto acid for use in this invention involves the condensation of the alkylated aromatic compound with an acylating agent in the presence of a Friedel-Crafts catalyst. The acylating agent is a dibasic acid compound having a total carbon content of from 4 to 20 carbon atoms, or more preferably of from 4 to 8 carbon atoms, and is a dibasic acid, a dibasic acid anhydride, or a dibasic acid halide.

Especially preferred for use in this invention are the keto acids derived by condensing alkyl aromatics and particularly paraffin wax alkylated naphthalene with succinic acid or with maleic acid or their anhydrides, in which case R will be CH CH respectively. A related keto acid that can be employed is that derived by condensing paraffin-wax-alkylated naphthalene or other alkylated aryl compound of the types disclosed, e.g. eicosyl benzene, with phthalic anhydride, in which case R will be a cyclic C radical. Other keto acids can be prepared by condensing the alkylated aryl compounds with dibasic acid halides; for example, the acid chlorides or mixed acid-acid chlorides of suberic acid, sebacic acid, adipic acid or azelaic acid. Specific acylating agents include, in addition to those already named, a-methyl pimelic acid, n-hexyl succinic acid, the di acid bromide of sebacic acid, the mono acid chloride of suberic acid, 1,14-tetradecane dicarboxylic acid, 5,5-diethyl glutaric acid, and 1,18-octadecane dicarboxylic acid.

The keto acid prepared from wax alkylated naphtha iene and maleic anhydride could have the formula:

O Wax CH=CHii-COOH In the alkylation of the aromatic compound with a halogenated aliphatic hydrocarbon, such as chlorinated paraffin Wax, it is possible to have two or more aromatic nuclei joined by aliphatic hydrocarbon linkages, so that the keto acids derived from the alkylated aromatics could have a formula of the following nature:

' ample:

R, R, and x having the same significance as in Formula 3.

It is believed that the keto acid prepared by condensing paraffin-wax-alkylated naphthalene with phthalic anaydride has the structure:

where R, x and n have the same significance as in Formula 3 above.

It will be understood, of course, that when halogenated paraffin wax or some other halogenated petroleum fraction is used, the alkylation product will be a complex mixture of alkylated aromatic compounds. The same will be true if alkylation has been done with a mixture of olefins.

The alkylation of the aromatic compound for the purpose of preparing an alkaryl keto acid for use in this invention may be conducted by any method known to the art. The most common alkylation procedure involves alkylation with either an olefinic hydrocarbon, e.g. a propylene polymer or an isobutylene polymer, or an alpha olefin from ethylene polymerization, or an alkyl halide, such as cetyl bromide, aided by a Friedel-Crafts catalysts, normally either AlCl or BF Other such catalysts include HF, AlBr polyphosphoric acid, etc.

The preparation of an alkylated naphthalene by the Friedel-Crafts condensation of a halogenated aliphatic hydrocarbon with naphthalene is well known and is disclosed, for example in US. Pats. 1,815,022 and 2,015,748. Briefly, the reaction involves the halogenation, (preferably chlorination) of an aliphatic hydrocarbon of from about 12 to about 32 carbon atoms until the product contains about to 15 wt. percent of chlorine. The halogenated material is then condensed with naphthalene in the presence of aluminum chloride or similar Friedel- Crafts catalyst. For example, paraffin wax or a petrolatum cut can be chlorinated at a temperature in the range of 140 to 300 F. until it contains 10 to 14% chlorine and it can then be condensed with naphthalene at 140 to 160 F. with the aid of a Friedel-Crafts catalyst. As a specific example, 9 parts of chlorinated paraffin wax can be condensed with one part of naphthalene, using as a catalyst 1 part by weight of aluminum chloride.

To prepare an alkaryl keto acid for use in this invention, about one mole of the wax alkylated naphthalene or similar alkylated aromatic hydrocarbon or alkylated phenol is condensed with from 1 to 2 moles of a dibasic acid or with an acid anhydride or with a dibasic acid halide as hereinbefore described in the presence of a Friedel-Crafts catalyst, such as AlCl BF FeCl or the like. In the case of the condensation of parafiin-waxalkylated naphthalene with maleic anhydride or with succinic anhydride, it is preferred that the reactants be used in about equimolar proportions. The condensation can be effected at temperatures ranging from about 20 F. to about 200 F., the preferred range being from about 30 F. to about 150 F. Reaction time may range from 1 to 12 hours and will usually require 3 to 8 hours. The mole proportion of Friedel-Crafts catalyst to acid anhydride may range from about 0.5 to 1 to about 2 to 1. It will generally range from about 0.5 to l to about 1.25 to 1.

For convenience in handling, it is preferred to dissolve the reactants in a suitable solvent such as orthodichloro benzene cyclohexane, normal heptane, or similar solvents having no tertiary hydrogen atoms. After the reaction has been completed, the resulting keto acid is Washed with dilute mineral acid, such as dilute hydrochloric acid, and water to remove the Friedel-Crafts catalyst.

It is possible to conduct the step of alkylating the aromatic hydrocarbon or related hydroxy derivatives and the step of converting the alkylated material to the keto acid in one operation, i.e. by reacting the aromatic hydrocarbon or the like with the alkylating agent, e.g. chlorinated parafiin wax or an alkyl halide, and with the acylating agent, e.g. the acid anhydride or acid halide, in the presence of a Friedel-Crafts catalyst, e.g. AlCl The reaction conditions employed in the step of condensing the keto acid with a polyalkylene polyamine are such as to favor the formation of amides with the carboxyl groups of the keto acids, although some of the product may contain Schiif base derivatives resulting from reaction with the keto groups. One or more of the amino groups of the polyamine will enter into either the amideforming reaction or the Schiff base forming reaction. Generally, the mole ratio of polyamine to keto acid will range from about 1:5 to about 3:1 although it is preferred that this ratio be in the range of from about /2 mole of polyamine per carboxylic acid group up to about 2 moles of polyamine per carboxylic acid group. The reaction temperatures for amide formation will generally be in the range from about 200 to 400 F. In most cases, however,

wherein n is 2 to 3 and m is a number from 0 to 10. Specific compounds coming within the formula include diethylene triamine, tetraethylene pentamine, dipropylene triamine, octaethylene nonamine, and tetrapropylene pentamine. N,N-di-(2-aminoethyl) ethylene diamine can also be used. Other aliphatic polyamine compounds that may be used are the N-aminoalkyl piperazines of the formula:

CHz-Cfil wherein n is a number 1 to 3, and R is hydrogen or an aminoalkyl radical containing 1 to 3 carbon atoms. Specific examples include .N-(Z-aminoethyl) piperazine, N42- aminoisopropyl) piperazine, and N,N'-di-(2-aminoethyl) piperazine.

The use of mixtures of alkylene polyamines, mixtures of N-arninoalkyl piperazines, and mixtures of the alkylene polyamines with the N-aminoalkyl piperazines is also contemplated.

The additives of this invention can be employed in concentrations ranging from about 0.001 to about wt. percent in oil compositions ranging from gasoline fractions through middle distillate fuels and lubricating oils.

For use as lubricating oil additives the reaction products of this invention will be incorporated in lubricating oil compositions in concentrations within the range of from about 0.1 to about 10 wt. percent and will ordinarily be used in concentrations of from about 0.1 to about 5 wt. percent. The lubricating oils to which the additives of the invention can be added include not only mineral lubrieating oils, but synthetic oils also. The mineral lubricat ing oils may be of any preferred types, including those derived from the ordinary paraflinic, naphthenic, asphaltic, or mixed base mineral crude oils by suitable refining methods. Synthetic hydrocarbon lubricating oils may also be employed. Other synthetic oils include dibasic acid esters such as di-Z-ethyl hexyl sebacate, carbonate esters, phosphate esters, halogenated hydrocarbons, polysilicones, polyglycols, glycol esters such as C oxo acid diesters of tetraethylene glycol, and complex esters as for example the complex ester formed by the reaction of 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2ethyl hexanoic acid.

The additives of this invention can also be employed in middle distillate fuels for inhibiting corrosion and the formation of sludge and sediment in such fuels. Concentration ranges of from about 0.002 to about 2 wt. percent, or more generally from about 0.005 to about 0.2 wt. percent are employed. Petroleum distillate fuels boiling in the range of from about 300 to about 900 F. are contemplated. Typical of such fuels are No. 1 and No. 2 fuel oils that meet ASTM Specification D-396-48T, diesel fuels qualifying as Grades 1D, 2D and 4D of ASTM Specification 13-975-5 1T, and various jet engine fuels. Because they are ashless, these additives are particularly desirable for such fuels in that they do not give rise to glowing ashes nor deter from the burning qualities of the distillates. These additives can also be used in conjunction with other prior art ashless additives for fuels, such as polymers of acrylic or methacrylic acid esters, high molecular weight aliphatic amines, etc.

The additives of this invention can also be employed either alone or in combination with other hydrocarbonsoluble additives, in jet fuels and gasolines in concentrations ranging from about 0.001 to 1.0 wt. percent as detergent and/ or rust preventive additives.

In either the fuel or lubricant compositions, other conventional additives may also be present, including dyes, pour-point depressants, antiwear agents, e.g. tricresyl phosphate, zinc dialkyl dithiophosphates of 3 to 8 carbon atoms, antioxidants such as phenyl-alpha-naphthylamine, tert. octylphenol sulfide, bis-phenols such as 4,4-methylene bis(2,6-di tert. butylphenol), viscosity index improvers such as polymethacrylates, polyisobutylene, alkyl fumarate-vinyl acetate copolymers, and the like as well as other dispersants.

The dispersant additives of the invention can be used to enhance the dispersancy-detergency of lubricants containing conventional detergents wherein the latter are used in concentrations in the range of about 0.5 to 5 Wt. percent. When the conventional detergents or dispersants are metal-containing materials it is possible, b utilizing the additives of the present invention in combination therewith, to obtain added dispersancy or detergency without materially increasing the total ash-forming properties of the composition. Such metal-containing detergents or combination detergent-inhibitors include the alkaline earth metal salts of alkylated phenols or of alkylated phenol sulfides, as for example barium-calcium nonyl phenol sulfide, the so-called basic alkaline earth metal sulfonates, and dispersions of barium carbonate or calcium carbonate in mineral oils containing various surfactants such as phosphosulfulized polyolefins, for example.

The sulfonates are well known in the art and are the oil-soluble alkaline earth metal salts of high molecular weight sulfonic acids obtained by sulfonating either natural or synthetic hydrocarbons. Specific examples of suitable sulfonates include calcium petroleum sulfonate, barium petroleum sulfonate, calcium di-C alkyl benzene sulfonate (C group from tripropylene), and barium C alkyl benzene sulfonate (C group from tetraisobutylene). The sulfonates may be of either the neutral type or of the over-based or high alkalinity type, containing metal base in excess of that required for simple neutralization, wherein the excess metal base has been neutralized with carbon dioxide.

Metal salts of alkyl phenols and of the alkyl phenol sulfides (i.e. alkyl phenol thioethers) are also Well known in the art. Metal salts of alkyl phenols having alkyl groups of from 5 to 20 carbon atoms are usually preferred, and the metal used to form the phenate is preferably an alkaline earth metal, e.g., calcium or barium, although the salts such as those of aluminum, cobalt, lead or tin are sometimes used. A specific example is the barium salt of the alkylation product of phenol with tripropylene. Metal salts of the corresponding alkyl phenol sulfides may also be used, e.g., barium tert. octyl phenol sulfide.

Other detergent additives include the reaction products of phosphosulfurized hydrocarbons with alkaline earth metal oxides or hydroxides, which can be prepared by first treating a hydrocarbon with a phosphorus sulfide and then reacting the product with an alkaline earth metal hydroxide or oxide, for example barium hydroxide, preferably in the presence of an alkyl phenol or an alkyl phenol sulfide and also preferably in the presence of carbon dioxide.

The dispersants of this invention may also be used in conjunction with other ashless detergents or dispersants such as high molecular weight polymeric dispersants made with one or more polar monomers, such as vinyl acetate, vinyl pyrrolidone, methacrylates, fumarates and maleates. These dispersants have molecular weights in the range of about 500 to 50,000. One example is a copolymer of 65 to wt. percent of mixed C to C fumarates, 10 to 20 wt. percent of vinyl acetate, and 5 to 15 wt. percent of N-vinyl pyrrolidone. Another example is the copolymer derived by reaction of mixed tallow alcohol fumarates and C oxo alcohol fumarates, averaging about 420 molecular weight, with vinyl acetate in a 3 to 1 acetatefumarate ratio, and 3 wt. percent of maleic anhydride, followed by subsequent removal of excess vinyl acetate. By tallow alcohol fumarates is meant the esters of fumaric acid and the alcohols derived by hydrogenation of tallow. The latter are principally C and C aliphatic alcohols with minor amounts of C C and C alcohols. C oxo alcohols are prepared by reaction of carbon monoxide and hydrogen on mixed C and C olefins, followed by hydrogenation of the resulting aldehydes.

The nature of this invention will be further understood when reference is made to the following examples, which include a preferred embodiment.

Example 1 The starting material for the preparation of a keto acid with a 50 wt. percent concentrate of a paraffin wax alkylated naphthalene in a solvent neutral mineral lubricating oil (viscosity 150 SUS at 100 F.). The parafiin wax alkylated naphthalene had been obtained by chlorinating a crude parafiin scale wax of 125 to 127 F. melting point to 14.5 wt. percent chlorine content and condensing 200 grams of the chlorinated wax with 25.6 grams of naphthalene with the aid of aluminum chloride catalyst- A 400 gram portion of the wax alkylated naphthalene concentrate was mixed with 100 cc. of orthodichloro benzene. Then 32 grams of aluminum chloride and 20 grams of maleic anhydride were added and the mixture was heated at 100 to 150 F. for about 4 hours. The product was then freed of aluminum chloride by washing it three times with percent hydrochloric acid solution in an amount equal in volume to the product and then with water until it was found to be acid-free. The orthodichloro benzene was then removed from the product by heating the latter to about 400 F. under vacuum (25 inches of Hg pressure). The active ingredient in the concentrate thus obtained was determined by infrared analysis to be a keto acid.

The entire quantity of keto acid product concentrate was condensed with 24.4 grams of tetraethylene pentamine in the presence of 400 ml. of toluene under reflux at a temperature of about 265 F. for 8 hours. The product was then filtered through Hyflo diatomaceous earth filter aid, and the toluene was removed by heating the product on a steam bath and stripping it with a stream of nitrogen. The final product concentrate in lubricating oil, containing about wt. percent of additive, was a very viscous waxy semi-solid melting at about 100 F. Analysis indicated that the concentrate contained 1.62 percent nitrogen by weight.

Example 2 A solution was prepared by adding 29.6 grams of naphthalene to 100 cc. of orthodichloro benzene at F. and to this was added 6 grams of aluminum chloride. Over a period of one hour, while the temperature was being raised from to 140 F., 200 grams of chlorinated parafiin wax was added. The chlorinated wax had been obtained by chlorinating a crude paraflin scale wax of 125 to 127 F. melting point to a content of 14.5 wt. percent chlorine. After all of the chlorinated wax had been added, the mixture was heated for three hours at 140 F. Following this step, the mixture was diluted with 200 grams of mineral lubricating oil, having a F. viscosity of 150 SUS. Then 32 grams of aluminum chloride was added, followed by 25 grams of maleic anhydride over a period of about 5 minutes, the temperature of the mixture being held at 117 to F.

The mixture was maintained at a temperature of 120 to F. for a period of three hours. The product was then treated to remove the aluminum chloride by adding 100 grams of normal hexane and thereafter subjecting it to three successive washes using 200 cc. of 2.5 normal HCl in each wash. This treatment was followed with three successive washes with hot water to remove residual acid. Then the mixture was heated to 400 F. at reduced pressure (25 inches of mercury) to remove the orthodichloro benzene, after which the mixture was reacted with 25 grams of tetraethylene pentamine in the same manner and under the same conditions as were used in Example 1. The resulting product, after removal of the toluene, was an additive concentrate having essentially the same properties as the product of Example 1.

Example 3 A complex was prepared by mixing 29.5 grams of phthalic anhydride, 400 ml. of orthodichloro benzene, and 30 grams of aluminum chloride. To this was added a 400 gram portion of the parafiin wax alkylated naphthalene concentrate that was employed in Example 1. The mixture was heated for five hours with stirring at 168 to 170 F. At the end of this time, the product was treated to remove aluminum chloride, using the same procedure as described in Example 1. Then the orthodichloro benzene solvent was removed from the mixture by heating at 400 F. under reduced pressure (25 inches of mercury).

The keto acid concentrate thus prepared was reacted with 30 grams of tetraethylene pentamine in the presence of 400 ml. of toluene under reflux at a temperature of about 265 F. for about eight hours. The product was then filtered and the toluene was removed as in Example 1, yielding a product concentrate containing about 50 wt. percent of additive and analyzing 1.1% nitrogen by weight.

Example 4 The procedure of Example 3 is repeated, substituting amine.

Example 5 A wax alkylated phenol was prepared in the following manner: 80 grams of the same chlorinated paraflin wax that was employed in Example 2 was mixed with 20.8 grams of phenol and 8 grams of aluminum chloride. It was then heated to about 120 F. for one hour, after which the temperature was raised to 165 F. Then an additional 226.8 grams of the same chlorinated wax was added over a 30-minute period. Following this, the temperature was increased to the range of 285 to 290 F. and held at that point for seven hours. Then the aluminum chloride was removed from the mixture, using hydrochloric acid and water washings in the same manner as described in Example 1. The yield of wax alkylated phenol was about 240 grams.

Then a mixture of 17 grams of aluminum chloride and 200 ml. of normal heptane was prepared and to this was added 12 grams of maleic anhydride at room temperature. After 30 minutes, to this mixture was added 120 grams of wax alkylated phenol as described above. The mixture was heated with stirring for five hours at F. The product was then subjected to washings with hydrochloric acid and water to remove the aluminum chloride in the same manner as described in the preceding examples. Subsequently, the heptane was stripped from the product by heating under vacuum. Then the product was reacted with 12 grams of tetraethylene pentamine in the presence of toluene in the same manner as described in Example 1. The product, after removal of the toluene, was a semi-solid material having a dark color.

Example 6 The procedure of Example 5 is repeated, substituting 10 grams of N-(Z-amino isopropyl) piperazine for the tetraethylene pentamine.

Example 7 A petroleum refinery stream consisting primarily of propylene is subjected to a conventional phosphoric-acidon-Kieselguhr polymerization process to give a product containing the trimer and tetramer of propylene. The product is fractionated and a cut boiling in the range of 360-400 F. and containing predominantly C olefins is contacted with silica-alumina catalyst to form the dimer of the tetra-propylene. The catalyst contains 12 wt. percent of A1 0 and 88% of SiO The feed is contacted with the catalyst at a temperature of 400 F., a pressure of 800 p.s.i.g., and a space velocity of one volume of feed per volume of catalyst per hour. The product is fractionated and is found to consist of 58% by volume of unconverted feed, 10 vol. percent of a fraction boiling in the range of 400-500 F., and 32 vol. percent of a fraction boiling at 500 F. and higher. The entire fraction boiling at 500 F. and higher is used to alkylate benzene in the presence of aluminum chloride catalyst. The alkylation conditions are 4/1 benzene to olefin ratio, a reaction temperature of 50-80 F. and 8 wt. percent of AlCl based on the olefin. The alkylate product boiling at 650 F. and higher has an aniline point of 150 F. and is found on mass spectrometry to contain 22 mol. percent of alkylated aromatic hydrocarbons having side chains containing 18 or less carbon atoms, 26 mol. percent having alkyl side chains in the C to C range, 23 mol. percent having C alkyl side chains, and 29 mol. percent having side chains of more than 24 carbon atoms. The average molecular weight of the alkylate is 391.

The mixture of alkylated aromatics obtained as just described is condensed with the mono acid chloride of suberic acid in approximately equal molar proportions as in the general procedure taught in Example 1. Two hundred grams of the resulting keto acid is then reacted with 8 grams of diethylene triamine in the presence of toluene under reflux at a temperature of about 265 F. for eight hours to form an amide.

Example 8 The starting material for this preparation is a cut of higher olefins containing from 20 to 28 carbon atoms obtained by the polymerization of ethylene. The cut contains 90 wt. percent of alpha olefins, 6 wt. percent of other olefins, and 4 wt. percent of saturated hydrocarbons, and predominates in C hydrocarbons (93%). It has a specific gravity of 0.798 at 68 F. Naphthalene is alkylated with this cut of higher olefins in the presence of a 'Friedel- Crafts catalyst. This is accomplished by dissolving 35 grams of naphthalene in 125 cc. of orthodichloro benzene and adding to this mixture 8 grams of aluminum chloride. To this mixture there is added 125 grams of the olefin fraction, and the temperature is raised to 110 F. After two hours at 110-120 F. the mixture is diluted with 200 grams of mineral lubricating oil having a 100 F. viscosity of 150 SUS. Then 35 grams of aluminum chloride is added, followed by 30 grams of maleic anhydride over a period of -10 minutes, the temperature of the mixture being held at about 120 F. After the mixture is maintained at a temperature of about 125 F. for three hours the product is treated to remove aluminum chloride and ortho-dichloro benzene in the same manner as described in Example 1. Then the keto acid product thereby obtained is condensed with 7 grams of triethylene tetrarnine in the presence of 450 ml. of toluene under reflux at a temperature of about 265 F. for seven hours. The product is then filtered and the toluene is removed, giving a product concentrate containing about 50 wt. percent of additive.

Example 9 A mixture is prepared, consisting of 50 grams of 1,2- dichloro dodecane, 78 grams of benzene, and 8 grams of AlCl After the mixture has been stirred for 1 hour at room temperature, 184 additional grams of 1,2-dichloro dodecane is added with stirring over a period of 30 minutes. Then the temperature is raised to 120-125 F. and maintained at that level for 5 hours. Following this, 100 grams of succinic anhydride and 133 grams of AlCl are added gradually over a 30 to 40 minutes period and the temperature is raised to about 160 F. and held there for about 7 hours.

The product is then treated with a mixture of ice and water to decompose the A101 and is subsequently dissolved in 500 cc. of heptane. The resulting solution is washed with three successive quantities of water (200 cc. each) and then dried over anhydrous magnesium sulfate. The keto acid thereby obtained is recovered by evaporating off the heptane.

The keto acid is converted to an amide by reacting 200 grams of the keto acid with grams of diethylene triamine at 250 F. for 6 hours while blowing a stream of nitrogen through the mixture to remove Water as it is formed.

10 Example 10 A mixture is prepared, consisting of grams of mono bromo octadecane, 94 grams of phenol, and 10 grams of AlC1 After the mixture has been stirred at about F. for one hour, the temperature is raised to about F., and 233 grams of additional mono bromo octadecane is gradually added over a /2 hour period. Heating and stirring are continued for 3 hours at about 160 F. Then 133 grams of AlCl and 202 grams of sebacic acid are added and the temperature is raised to 200 F. and held there for 5 hours.

The reaction mixture is then treated with ice water, dissolved in heptane, and subjected to water washings as described in Example 9, and the heptane removed to give the keto acid. To convert the keto acid to an amide product, 300 grams of the keto acid and 12 grams of triethylene tetramine are reacted at 300 F. for 3 hours while blowing a stream of nitrogen through the mixture.

Example 11 The procedure of Example 1 was repeated, but substituting 20 grams of succinic acid anhydride for the 20 grams of maleic anhydride in the preparation of the keto acid, and employing 30 grams of tetraethylene pentamine rather than the 24.4 grams used in Example 1 in the step of condensing the keto acid with the polyamine. Conditions and proportions were otherwise the same as in Example 1. The resulting additive concentrate, containing about 50 weight percent of additive, was found on analysis to contain 1.05 wt. percent nitrogen.

Example 12 Using as the base oil a mineral lubricating oil having a viscosity of 325 SUS at 100 F. and a viscosity index of about 100, the following compositions were prepared:

Composition 1.-3.5 ft. percent of a commercial detergent inhibitor, 0.9 wt. percent of a zinc dialkyldithiophosphate antiwear additive and 95.6 wt. percent of the base oil.

Composition 2.-3.5 wt. percent of the same detergent inhibitor and 0.9 wt. percent of the same antiwear additive as in Composition 1, along with 2 wt. percent of the product of Example 1 and 93.6 wt. percent of the base oil (sufficient additive to give 1% active ingredient).

Composition 3.3.5 wt. percent of the same detergent inhibitor and 0.9 wt. percent of the same antiwear additive as in Composition 1, along with 2 wt. percent of the product of Example 3 and 93.6 wt. percent of the base oil (sufiicient additive to give 1% active ingredient).

Composition 4.3.5 wt. percent of the same detergent inhibitor and 0.9 wt. percent of the same antiwear additive as in Composition 1, along with 2 wt. percent of the product of Example 5 and 93.6 wt. percent of the base oil (sufiicient additive to give 1% active ingredient).

The commercial detergent inhibitor mentioned above was a mineral oil solution containing an additive prepared by reacting a mixture of phosphosulfurized polyisobutylene and nonyl phenol with barium hydroxide pentahydrate and blowing the reaction mixture with. carbon dioxide. The approximate analysis of the concentrate is 27 wt. percent of phosphosulfurized polyisobutylene, 11.7 wt. percent nonyl phenol, 10.6 Wt. percent bariu moxide, 2.5 wt. percent carbon dioxide, and 48.2 wt. percent of mineral oil.

The zinc dialkyldithiophosphate antiwear additive was an oil solution consisting of about 25 wt. percent of mineral lubricating oil and about 75 wt. percent of zinc dialkyldithiophosphate prepared by treating a mixture of isobutanol and mixed amyl alcohols with P 8 followed by neutralizing with zinc oxide.

Each of the compositions was tested for sludge dispersing ability in a Cyclic Temperature Sludge Test which, from prior experience, has been shown to give sludge deposits similar to those obtained in stop-and-go driving such as would be experienced in taxicab operation. Briefly described, in this test a Ford 6-cylinder engine in run on a dynamometer stand through alternate cycles, the first cycle lasting hours, at 1500 r.p.m., and the second cycle lasting 2 hours, at the same operating speed, with the oil sump and water jacket temperatures being slightly higher in the second cycle than in the first. The two cycles are alternated in sequence until the desired total test time has clasped. Make-up oil is added as required so as to maintain the oil level in the crankcase at all times between about 3' /2 and 4 quarts. At the end of selected periods of test time, the engine is inspected by disassembling it sufliciently to permit visual examination of several of the parts, including the rocker arm assembly, the rocker arm cover, the cylinder head, the push rod chamber and its cover, the crankshaft and the oil pan. These parts are visually and quantitatively rated for sludge deposits, using a CRC Sludge Merit rating system in which a numerical rating of represents a perfectly clean part, and the numerical scale decreases to a minimum value representing a part covered with the maximum amount of sludge possible. The several merit ratings are average to give an overall engine merit rating.

The results of the cycle temperature sludge test are summarized in Table I. It will be seen from these results that incorporation of the additive products of the present invention greatly increased the ability of the oil composition to disperse sludge.

TABLE I.-SLUD GE MERIT RATINGS-CYCLIC TEMPERA- TURE TEST A blend was prepared by adding to a refined neutral lubricating oil derived from Pennsylvania crude oil sufficient of the concentrate of Example 1 to supply 3 wt. percent of the additive material in the concentrate.

The base oil had a viscosity of 146.7 SUS at 100 F. and of 42.9 SUS at 210 F. A second blend was prepared by adding to another portion of the same base oil sufficient of the wax alkylated naphthalene concentrate of Example 1 to furnish 3 wt. percent of wax alkylated naphthalene in the blend.

The pour points of each blend, as well as the pour point of the base oil were determined. The results are shown in Table II.

TABLE II Pour Point, F. Base oil +35 Base oil plus 3% wax alkylated naphthalene 0 Base oil plus 3% Example 1 product -35 1 Actual additive basis.

EXAMPLE 14 A lubricant composition suitable for use as a railroad diesel engine lubricant is prepared by blending 2.0 wt. percent of the concentrate additive of Example 1 and 0.4 wt. percent of phenyl alpha naphthylamine in a base stock consisting of a hydrofined and phenol extracted coastal oil. The blend has a viscosity of 1016 SUS at 100 F.

EXAMPLE 15 To a heating oil comprising a mineral oil distillate having a boiling range of about 350 to 680 F. and derived from mixed cracked and straight run distillates is added 0.02 wt. percent of the concentrate product of Example 5.

12 EXAMPLE 16 A compounded lubricant suitable for use as a crankcase oil is prepared by blending with a light mineral base oil having a sufficient quantity of an added viscosity index improver to place it in the ISAE 10W-30 viscosity class, 2.5 wt. percent of the cencentrate of Example 3, 1.1 wt. percent of a high alkalinity barium sulfonate (60 total base number) derived from hydrocarbon sulfonic acids of 440 average molecular weight and 0.65 -wt. percent of zinc dialkyldithiophosphates derived from mixed C C and C alcohols.

EXAMPLE 17 About 0.007 wt. percent of the concentrate of Example 2 is added by simple mixing to a leaded gasoline for the purpose of imparting rust preventive properties and carburetor detergency action thereto. The gasoline has an initial boiling point of 90 F., a 50% point of 208 F., and a final boiling point of 378 F. (ASTM D-86), and contains 17 vol. percent aromatics, 13 vol. percent olefins, and vol. percent saturated hydrocarbons.

It is within the contemplation of this invention to prepare additive concentrates in which the concentration of additive is greater than would normally be employed in a finished lubricant. These concentrates may contain in the range of from 10 to of additive on an active ingredient basis, the balance being mineral oil. Such concentrates are convenient for handling the additive in the ultimate blending operation into a finished lubricating oil composition. The additive concentrates can be made up simply of an additive of the present invention in a suitable mineral oil medium or they can include other additives that are intended for use along with the additives of the invention in a finished lubricant. Thus, if the additives are to be used in conjunction with conventional detergents, an additive concentrate can be prepared containing say 30 to 60 wt. percent of an additive of the invention and 5 to 20 wt. percent of a metal sulfonate, e.g., calcium petroleum sulfonate from sulfonic acids of about 450 molecular weight, or a metal alkylphenol sulfide, e.g., calcium nonylphenol sulfide, with the balance being a mineral lubricating oil. Additionally, 5 to 15 wt. percent of an antiwear agent such as a zinc dialkyldithiophosphate, e.g., mixed zinc butyl and amyl dithiophosphates may also be present in the additive concentrate package.

While the lubricant compositions herein described are primarily designed as internal combustion engine crankcase lubricants, the additives of the invention may also be employed in other oil compositions, including turbine oils, various industrial oils, gear oils, hydraulic fluids, transmission fluids and the like.

It is to be understood that the examples presented herein are intended to be merely illustrative of the invention and not as limiting it in any manner; nor is the invention to be limited by any theory regarding its operability. The scope of the invention is to be determined by the appended claims.

What is claimed is:

1. The oil-soluble product obtained by reacting a polyamine with an alkaryl keto acid at a temperature of from about 200 to 400 F. for a sufficient period of time to split out water and form an amide, using a molar proportion of polyamine to acid in the range of about 1:5 to about 3:1;

said alkaryl keto acid having been prepared by alkylating an aromatic compound of from 6 to 16 carbon atoms, selected from the group consisting of unsubstituted aromatic cyclic hydrocarbons, monohydroxy derivatives thereof, short-chain alkylated aromatic cyclic hydrocarbons, and monohydroxy derivatives thereof, with an aliphatic compound of from 12 to 32 carbon atoms, selected from the group consisting of olefinic hydrocarbons and saturated halogenated aliphatic hydrocarbons, and by condensing the resulting alkylated aromatic material, at from 20 F 13 to 200 F., in the presence of a Friedel-Crafts catalyst with an acylating agent having from 4 to 20 carbon atoms, said acylating agent being a dibasic acid of the formula R(COOH) or the corresponding dibasic acid halide or dibasic acid anhydride, wherein R is alkylene of 2 to 18 carbon atoms, alkenylene of 2 to 6 carbon atoms, or phenylene; said polyamine being selected from the class consisting of N,N-di-(2-almino ethyl) ethylene diamine, an alkylene polyamine having the formula:

wherein n is 2 to 3 and m is a number from 0 to 10, and an N-aminoalkyl piperazine of the formula:

CHz-CHz N-R CH2-C] E[z wherein n is a number 1 to 3 and R is selected from the group consisting of hydrogen and an aminoalkyl radical of 1 to 3 carbon atoms.

2. Product as defined by claim 1 wherein said alkylated aromatic material has been obtained by alkylating said aromatic compound with halogenated parafiin wax.

3. Product as defined by claim 1 wherein said acylating agent is maleic anhydride.

4. Product as defined by claim 1 wherein said acylating agent is phthalic anhydride.

5. Product as defined by claim 1 wherein said acylating agent is succinic acid anhydride.

6. Product as defined by claim 1 wherein said aliphatic polyamine is tetraethylene pentamine.

7. Product as defined by claim 1 wherein said aliphatic polyamine is diethylene triamine.

8. Product as defined by claim 1 wherein said aromatic compound that is alkylated is naphthalene.

9. Product as defined by claim 1 wherein said aromatic compound that is alkylated is benzene.

10. Product as defined by claim 1 wherein said aromatic compound that is alkylated is phenol.

References Cited UNITED STATES PATENTS 4/1940 Reifl.

HENRY R. JILES, Primary Examiner N. TROUSOF, Assistant Examiner US. Cl. X.R. 

